Pseudo-azimido-benzene-amino-acyloacetic acid esters



Patented Nov. 8, 1938 UNITED STATES 2,136,135 PSEUDO-AZllVlIDO-BENZENE-AMINO ACYL- OAGETIG ACID ESTERS Hans Johner and Gerald Bonhote, Basel, Switzerland, assignors to the firm Society of Chemical Industry in Basle, Basel, Switzerland 1 8 Claims.

The present invention relates to new arylides of Ji-ketone-carboxylic acids which are valuable intermediate products for the manufacture of dyestuffs. It comprises the new arylides, the

process of producing the same as well as their application for the manufacture of dyestuffs.

It has been found that valuable arylides of piketone-carboxylic acids may be obtained if amino compounds of the general'formula in which R. stands for an aryl radical of the benzene or naphthalene series such as the 5-amino- 2-phenyl-pseudo-azimidobenzene, the 5 -'ain'ino 6-methyl-2-phenyl-pseudo azimidobenzene, the 5-amino-2-(4'-methoxy) -phenyl-p'seudo azimidobenzene, the 5-amino-2(4- ethoxy) phenylpseudo-azimidobenzene, the 5-ami'no-6-methy1- 2- (4'-methoxy) -phenyl-pseudo azimidobenzene, the 5-amino-6-methyl 2 -"(4'- ethoxy) -p-henylpseudo-azimidobenzene, the 5-amino-6-methoxy- 2- (4' -methoxy) phenyl-pseudo-azimidobenzene, the 5-amino-6-methoxy-2- (4 ethoxy) phenylpseudo azimidobenzene, the 5 amino 2 -(1') naphthyl-pseudo-azimidobenzene, the E-amino- 2- (4-c-methoxy-oxyethyl) phenyl pseudo-azimidobenzene, are condensed with esters of B- ketone-carboxylic acids, such as ethyl acetoacetate, benzoyl acetic ester, or terephthaloyl acetic ester,

These arylides thus correspond to the general formula in which R stands for a member of the group consisting of aryl nuclei of the benzene and naphthalene series, R1 stands for a member of the group consisting of methyl and phenyl, and y stands for a member of the group consisting of H, CH3 and O-alkyl. Among such products those are valuable in which R represents a nucleus of the benzene series because they lead to particularly valuable dyestuffs. Among such products those are again particularly valuable which correspond to the general formula in which y has the signification already indicated above and :1 stands for a member of the group No Drawing. Application July 12, 1937, Serial In Switzerland July 14, 1936 consisting of H, CH3 and O-alkyl. All these products are light colored powders insoluble in water but soluble in aqueous caustic alkalies.

The new arylides, which represent valuable intermediate products for the manufacture of dyestuffs, dissolve in aqueous caustic alkalies owing to the presence of the -COCH2CO- group. In such solutions the alkali salts of the new arylides possess a marked affinity for the Vegetable fiber, which is entirely surprising, since the similar arylides from the isomeric amino-azimides do not possess such an afiinity for the vegetable fiber. Since they combine with diazo compounds to azo-dyestuffs they are inter alia very suitable for the production of azo-dyestuffs on the vegetable fiber (cotton, ram-ie, flax, jute and the like) as well as on regenerated cellulose (viscose or cuprammonium silk), and also on animal fibers such as wool, natural silk or loaded silk, according to the methods usual in dyeing with ice colours. Such methods are, for example, padding the fiber in an alkaline solution of the new arylide and developing with a diazo compound, preferably one containing no hydroxy-, carb'oxyor sulfo-groups. Such diazo-compounds are, for instance, those derived from aniline, ethers or esters of amino-phenols, for example orthoor para-anisidine, 4-chloroZ-amino-diphenylether, 4:4'-dichloro-2-aminodiphenylether; those derived from monoacylated products from 2:5-diaminohydro-quinone-diethylor -dimethy1ether and benzoylchloride or phenoxy-acetic-acidchloride; aminoazo dyestuffs, for instance, 4- amino-5-methoxyazobenzene, l-amin'o 2:5 dimethoxyazobenzene, ortho-amino-azo toluene; further those derived from chlorotoluidines, for instance l-chloro-2-methyl-l-aminobenzene, 4- chloro-1-methyl-2-aminobenzene; those from ni-' tranalines such as ortho-nitraniline, 1-amino-2- methylA-nitrobenzene, l-amino-2-n'itro-4-chlorobenzene, 1-amino-2-nitro-4-1nethylor -methoxybenzene, or 4-nitro-2-methoxy-1-aminoben zene; those derived from orthoor meta-chloraniline, 2:5-dich1oraniline, uor ,c naphthylamine and the like.

For the purpose of producing fast tints on the fiber preparations or printing colors containing them may also be prepared which contain an alkali salt of the new derivatives and a stabilized diam-compound in the form of a nitrosamine or of a diazoamino-compound. These preparations may be printed on the fiber and then developed to dyestuifs by suitable treatment, for example by passage through an acid. It is also possible to print mixtures of the free diazotizing components or the corresponding Nnitramines and alkali salts of the new coupling components on the fiber and to convert such mixture into dyestufis by development with nitrous acid, and, if desired, subsequent treatment in alkali.

The condensation products of the general formula in which R, R1 and y have the signification indicated above, coupled in substance with the same non-sulfonated compounds with which they are used for the production of fast tints on the fiber, yield pigments which are useful as such or in coloring lacquers, varnishes or the like.

With sulfonated diazo-compounds wool dyestuffs are in particular obtained. Especially valuable are the dyestuffs which are derived from ortho-hydroxylated or ortho-carboxylated diazoare added gradually 15 parts of ethylacetoacetate. Condensation is continued for 2 hours, during which time the alcohol formed and some chlorobenzene are distilled. When condensation is complete, the mass is cooled, the chlorobenzene is distilled in steam and the condensation prodnot left behind is filtered; it is dissolved in dilute caustic alkali lye and, after filtration from some impurities, the solution is treated with dilute hydrochloric acid to reprecipitate the condensation product.

It is a white powder freely soluble in dilute alkalies and melting after recrystallization from alcohol at 152 C.

The process is similar with the other pseudoazimides and fi-ketone-carboxylic acid esters cited in the introductory paragraphs. The following table shows the melting point of some of such condensation products:

B-ketone-carboxylic-acid-ester Azimide Melting point from- Ethyl acetoacetate +5-ami n0-2-(4-methoxy)-phenyl-pseudo-azimidobenzene.; Alcohol 163 0. Do +5-am1 no-2-(4-ethoxy)-phenyl-pseudo-azimidobenzene Alcohol 191 0. Do +5-am1no-6*methyl-2-phenyl-pseudo-azimidobenzene Alcohol 205 0. Do +5 a 6 methyl 2 (4 methoxy) phenyl pseudo- Chlorobenzene 222 0. az1m dobenzene. Do +-an 11no-6-methoxy-2-(4-methoxy)-phenyl-pseudo-azi- Alcohol 168 C.

midobenzene. Do +5-ammo-6-methoxy-2-(4-ethoxy)-phenyl-pseudo-azimi- Alcohol 155 C.

dobenzene. +5-amino-6-ch1oro-2-phenyl-psoudo-azimidobenzene Alcohol 185 0. Do +5-am1n0-6-met y1- )mapllthyl-pseudo-azimidobenzene Ohlorobenzene 209 C. Benzoyl acetic ester. +5-am1no-2-phenyl-pseudo-azimidobenzene Alcohol 180 C. Terephthaloyl-diacetic ester ..do 7 Alcohol 280 0.

compounds as these products may be converted in substance or on the fiber into metalliferous dyestuffs.

The dyestuffs which may be prepared according to the present process with aid of the new arylides correspond therefore to the general formula r in which R, R1 and y have the signification indicated above, and R2 stands for an aromatic radical selected from the group consisting of aromatic nuclei of the benzene and naphthalene series. If these dyestuffs do not contain sulfogroups they represent yellow to orange or brownorange pigments which are insoluble in water. Particularly valuable are the dyestuffs of the formula in which R2 stands for an aromatic radical of the benzene series, if the benzene radical R2 contains a Intro-group in ortho-position to the -N=N-group. These dyestuffs when produced on the fiber dye the same yellow tints of very good fastness properties, particularly excellent fastness to light.

The following examples illustrate the invention, the parts being by weight:-

Example 1 21 parts of 5-amino-2-phenyl-pseudo azimidobenzene are introduced into 200 parts of chlorobenzene, a few drops of diethylaniline are added and the whole is heated to boiling under reflux.

The chlorobenzene is then distilled and. there Example 2 13.87 parts of ortho-nitraniline are diazotized as usual and the product is introduced into a solution of 29.4 parts of the condensation product from 5-amino-2-pheny1-pseudo-azimidobenzene and ethylacetoacetate, 100 parts of sodium hydroxide solution of 36 B., 1 5 parts sodium acetate and 2000 parts of 'water. The yellow dyestuff formed is precipitated immediately; it is filtered and dried.

If a sulfonic acid, for instance sulfanilic acid, is substituted for the ortho-nitraniline, there is obtained a dyestuif soluble in water.-

Ewample 3 Cotton yarn is impregnated with a grounding prepared by dissolving 3 parts of the condensation product from 5aminophenyl-pseudo-azimidobenzene and ethylacetoacetate in 300 parts of hot water with the addition of 6 parts sodium hydroxide solution of 30 per cent. strength, 10 parts of Turkey red oil, parts of sodium chloride, and water to make up 1000 parts. The goods are then wrung out and developed in a diazo-solution which has been neutralized with sodium acetate and acidified with acetic acid, and corresponds with 2 parts of 1-amino-2- methyl-l-nitrobenzene per 1000 parts. There is produced a pure greenish-yellow of very good properties of fastness.

Similar tints are obtained with other diazocomponents, for instance 1-amino-2-methyl-4- chlorobenzene, 1-amino-2-nitro-4-chlorobenzene, 1-amino-2-nitro-4-methylbenzene. Redder tints are obtained for instance with l-amino-Z-nitrol-methoxybenzene or ortho-aminoa'zotoluene.

The goods may also be grounded at a raised temperature, for instance at 80 C.; such arylides may also be used for printing.

The following table comprises a number of for the Vegetable fiber, and react with diazo cominvention pounds with formation of azo-dyestufis.

DiaZo-component Condensation product from ethyl-aceto-acetate with- Color Ortho-nitraniline 5-amino-2-(4-methoxy)-phenyl-pseudo-azimidobenzene Yellow. l-amino-Z-nitro-4methyl-benzene do- Do. 1-amino-2-nitro-4methoxybenzenedo Do.

5-amino-2-(4-etl1oxy)-phenyl-pseudo-azimidobenzene D Ortho-nitramline Para-mtraniline.

Ortho-aminoaZo-toluene l-amino-2-nitro-4-chlorbenzene 2:5-dichlotaniline 4:4-dichlor-2-aminodipl1enyletl1er-- 1-amino-2-nitr0-4-chlorbenzene Ortho-nitraniline o. Greenish-yellow. Reddish-yellow.

5-smino-6-methyl-2-phenyl-pseudo-azimidobenzene Gold-orange. 5-%mino-6-methyl-2- (4 -mcthoxy) -phenyl-pseudo-azimido- Reddish-yellow.

enzene. fi-amino-S-methoxy-Z-(4-metl1oxy)-phenyl-pseudo-azimido- Yellow.

benzene. do Greenish-yellow. do Reddish-yellow. do Yellow.

What we claim is: 1. As new products the arylides of the general formula in which R stands for a member of the group consisting of nuclei of the benzene and naphthalene series, R1 stands for a member of the group consisting of methyl and phenyl, and 3 stands for a member of the group consisting of H, CH3 and O-alkyl, which products are light colored powders, dissolving in aqueous caustic alkalies, from which solutions they possess affinity for the vegetable fiber, and react with diazo compounds with formation of azo-dyestuffs.

2. As new products the arylides of the general formula in which R1 stands for a member of the group consisting of methyl and phenyl, y stands for a member of the group consisting of H, CH3 and O-alkyl, and it stands for a member of the group consisting of H, CH3 and O-alkyl, which products are light colored powders, dissolving in aqueous caustic alkalies, from which solutions they possess affinity for the vegetable fiber, and react with diazo compounds with formation of azo-dyestuifs.

3 As new products the arylides of the general formula in which :1] stands for a member of the group consisting of H, CH3 and O-alkyl, and :0 stands for a member of the group consisting of H, CH3, 0'- alkyl and halogen, which products are light colored powders, dissolving in aqueous caustic alkalies, from which solutions they possess aflinity l II o N-C-CHr- OH;

4. As new products the arylides of the general formula i i i N-C-OHrC-CHB in which y stands for a member of the group consisting of H, CH3 and O-alkyl, which products are light colored powders, dissolving in aqueous caustic alkalies, from which solutions they possess affinity for the vegetable fiber, and react with diazo compounds with formation of a20- dyestuffs.

5. As new products the arylides of the general formula in which the alkyl-group contains not more than 2 carbon atoms, and in which :1 stands for a member of the group consisting of H, CH3 and O-alkyl, which products are light colored powders, dissolving in aqueous caustic alkalies; from which solutions they possess afiinity for the vegetable fiber, and react with diazo compounds with formation of azo-dyestuffs.

6. As a new product the arylide of the formula HANS JOI-INER. A GERALD BONHOTE. 

